公开(公告)号：US20120318050A1

公开(公告)日：2012-12-20

申请号：US13526932

申请日：2012-06-19

申请人： Craig M. Whitehouse ,  Thomas White

发明人： Craig M. Whitehouse ,  Thomas White

IPC分类号： H01J49/26 ,  G01N1/00

CPC分类号： B01D59/44 ,  G01N1/4005 ,  G01N30/00 ,  G01N30/7266 ,  H01J49/165 ,  Y10T436/212 ,  Y10T436/24

摘要： A method and apparatus to trap, release and/or separate sample components in solution passing through a channel with or without packing material present by passing ion current through the channel driven by an electric field. A portion of the ion current includes cation and/or anion species generated from second solution flows separated from the sample solution flow path by semipermeable membranes. Cation and/or anion ion species generated in the second solution flow regions are transferred into the sample solution flow path through ion selective semipermeable membranes. Ion current moving along the sample solution flow path is controlled by varying the composition of the second solutions and/or changing the voltage between membrane sections for a given sample solution composition. The sample composition may also be varied separately or in parallel to enhance trapping, release and/or separation efficiency and range.

摘要翻译： 一种方法和装置，其通过使离子流通过由电场驱动的通道而使通过具有或不具有填充材料的通道通过通道的溶液中的样品组分被捕获，释放和/或分离。 离子电流的一部分包括由通过半透膜从样品溶液流动路径分离的第二溶液流产生的阳离子和/或阴离子物质。 在第二溶液流动区域中产生的阳离子和/或阴离子物质通过离子选择性半透膜转移到样品溶液流动路径中。 通过改变第二溶液的组成和/或改变给定样品溶液组合物的膜部分之间的电压来控制沿样品溶液流动路径移动的离子电流。 样品组合物也可以单独地或并行地改变以提高捕获，释放和/或分离效率和范围。

公开(公告)号：US07619216B1

公开(公告)日：2009-11-17

申请号：US11803984

申请日：2007-05-15

申请人： Craig M. Whitehouse ,  Thomas White

发明人： Craig M. Whitehouse ,  Thomas White

IPC分类号： B01D59/44 ,  G01N24/00

CPC分类号： H01J49/165 ,  B01D61/00 ,  B01D61/425 ,  B01D2313/345 ,  G01N30/7266 ,  H01J49/0018 ,  H01J49/167 ,  Y10T436/212 ,  Y10T436/24

摘要： Charged droplet spray is formed from a solution with all or a portion of the charged droplet spray current generated from reduction or oxidation (redox) reactions occurring on surfaces removed from the first or sample solution flow path. In one embodiment of the invention, two solution flow channels are separated by a semipermeable membrane. A first or sample solution flowing through the first solution flow channel exchanges cation or anion charged species through the semipermeable membrane with a second solution or gas flowing through the second flow channel. Charge exchange is driven by the electric field applied at the charged droplet sprayer sample solution outlet. Redox reactions occur at an electrode surface in contact with the second solution. The second solution or gas phase composition can be changed as a step function or as a gradient to run pH or conductivity scans in the first solution to optimize or modify Electrospray performance in Electrospray mass spectrometry applications. The first or sample solution forms a charged droplet spray by Electrospray or pneumatic nebulization in the presence of an electric field from the first solution flow channel exit. Evaporating charged liquid droplets form ions from species in solution that are transferred into vacuum and mass to charge analyzed. The second solution or composition can be modified to selectively change pH, conductivity and/or composition of the sample solution during Electrospray ionization to enhance or extend analytical performance for given ES/MS analytical applications. The invention increases the control and range of the Electrospray ionization process during ES/MS operation. Alternative embodiments of the invention provide for conducting redox reactions on conductive surfaces removed from the first or sample solution flow path but not separated by semipermeable membranes.

摘要翻译： 由溶液形成带电的液滴喷雾，其中从在第一或样品溶液流动路径上去除的表面上发生的还原或氧化（氧化还原）反应产生的全部或一部分带电液滴喷雾电流。 在本发明的一个实施方案中，两个溶液流动通道被半透膜隔开。 流过第一溶液流动通道的第一或样品溶液通过半透膜与穿过第二流动通道的第二溶液或气体交换阳离子或阴离子带电物质。 电荷交换由在带电液滴喷雾器样品溶液出口处施加的电场驱动。 在与第二溶液接触的电极表面处发生氧化还原反应。 可以将第二溶液或气相组合物作为步骤功能或梯度来改变以在第一溶液中进行pH或电导率扫描，以优化或改变电喷雾质谱法应用中的电喷雾性能。 第一或样品溶液在来自第一溶液流动通道出口的电场的存在下通过电喷雾或气动雾化形成带电的液滴喷雾。 蒸发的带电液滴从溶液中的物质形成离子，转移到真空中并进行质量分析。 可以修改第二种溶液或组合物以在电喷雾离子化期间选择性地改变样品溶液的pH，电导率和/或组成，以增强或扩大给定的ES / MS分析应用的分析性能。 本发明增加了ES / MS操作期间电喷雾电离过程的控制和范围。 本发明的替代实施例提供了在从第一或样品溶液流动路径移除但不被半透膜隔离的导电表面上进行氧化还原反应。

公开(公告)号：US07232992B2

公开(公告)日：2007-06-19

申请号：US11132953

申请日：2005-05-19

申请人： Craig M. Whitehouse ,  Thomas White

发明人： Craig M. Whitehouse ,  Thomas White

IPC分类号： B01D59/44 ,  G01N24/00

CPC分类号： H01J49/165 ,  B01D61/00 ,  B01D61/425 ,  B01D2313/345 ,  G01N30/7266 ,  H01J49/0018 ,  H01J49/167 ,  Y10T436/212 ,  Y10T436/24

摘要： Charged droplet spray is formed from a solution with all or a portion of the charged droplet spray current generated from reduction or oxidation (redox) reactions occurring on surfaces removed from the first or sample solution flow path. In one embodiment of the invention, two solution flow channels are separated by a semipermeable membrane. A first or sample solution flowing through the first solution flow channel exchanges cation or anion charged species through the semipermeable membrane with a second solution or gas flowing through the second flow channel. Charge exchange is driven by the electric field applied at the charged droplet sprayer sample solution outlet. Redox reactions occur at an electrode surface in contact with the second solution. The invention increases the control and range of the Electrospray ionization process during ES/MS operation. Alternative embodiments of the invention provide for conducting redox reactions on conductive surfaces removed from the first or sample solution flow path but not separated by semipermeable membranes.

摘要翻译： 由溶液形成带电的液滴喷雾，其中从在第一或样品溶液流动路径上去除的表面上发生的还原或氧化（氧化还原）反应产生的全部或一部分带电液滴喷雾电流。 在本发明的一个实施方案中，两个溶液流动通道被半透膜隔开。 流过第一溶液流动通道的第一或样品溶液通过半透膜与穿过第二流动通道的第二溶液或气体交换阳离子或阴离子带电物质。 电荷交换由在带电液滴喷雾器样品溶液出口处施加的电场驱动。 在与第二溶液接触的电极表面处发生氧化还原反应。 本发明增加了ES / MS操作期间电喷雾电离过程的控制和范围。 本发明的替代实施例提供了在从第一或样品溶液流动路径移除但不被半透膜隔离的导电表面上进行氧化还原反应。

公开(公告)号：US08455817B2

公开(公告)日：2013-06-04

申请号：US13526932

申请日：2012-06-19

申请人： Craig M. Whitehouse ,  Thomas White

发明人： Craig M. Whitehouse ,  Thomas White

IPC分类号： B01D59/44 ,  G01N24/00

CPC分类号： B01D59/44 ,  G01N1/4005 ,  G01N30/00 ,  G01N30/7266 ,  H01J49/165 ,  Y10T436/212 ,  Y10T436/24

摘要： A method and apparatus to trap, release and/or separate sample components in solution passing through a channel with or without packing material present by passing ion current through the channel driven by an electric field. A portion of the ion current includes cation and/or anion species generated from second solution flows separated from the sample solution flow path by semipermeable membranes. Cation and/or anion ion species generated in the second solution flow regions are transferred into the sample solution flow path through ion selective semipermeable membranes. Ion current moving along the sample solution flow path is controlled by varying the composition of the second solutions and/or changing the voltage between membrane sections for a given sample solution composition. The sample composition may also be varied separately or in parallel to enhance trapping, release and/or separation efficiency and range.

摘要翻译： 一种方法和装置，其通过使离子流通过由电场驱动的通道而使通过具有或不具有填充材料的通道通过通道的溶液中的样品组分被捕获，释放和/或分离。 离子电流的一部分包括由通过半透膜从样品溶液流动路径分离的第二溶液流产生的阳离子和/或阴离子物质。 在第二溶液流动区域中产生的阳离子和/或阴离子物质通过离子选择性半透膜转移到样品溶液流动路径中。 沿着样品溶液流动路径移动的离子电流通过改变第二溶液的组成和/或改变给定样品溶液组合物的膜部分之间的电压来控制。 样品组合物也可以单独地或并行地改变以提高捕获，释放和/或分离效率和范围。

公开(公告)号：US20090095900A1

公开(公告)日：2009-04-16

申请号：US12251058

申请日：2008-10-14

申请人： Craig M. Whitehouse ,  Thomas White ,  Shida Shen

发明人： Craig M. Whitehouse ,  Thomas White ,  Shida Shen

IPC分类号： B01D59/44

CPC分类号： H01J49/165 ,  Y10T436/24

摘要： Electrospray ionization sources interfaced to mass spectrometers have become widely used tools in analytical applications. Processes occurring in Electrospray (ES) ionization generally include the addition or removal of a charged species such as H+ or other cation to effect ionization of a sample species. Electrospray includes ionization processes that occur in the liquid and gas phase and in both phases ionization processes require a source or sink for such charged species. Electrolyte species, that aid in oxidation or reduction reactions occurring in Electrospray ionization, are added to sample solutions in many analytical applications to increase the ion signal amplitude generated in Electrospray and detected by a mass spectrometer (MS) Electrolyte species that may be required to enhance an upstream sample preparation or separation process may be less compatible with the downstream ES processes and cause reduction in MS signal. New Electrolytes have been found that increase positive and negative polarity analyte ion signal measured in ESMS analysis when compared with analyte ESMS signal achieved using more conventional electrolytes. The new electrolyte species increase ES MS signal when added directly to a sample solution or when added to a second solution flow in an Electrospray membrane probe. It has also been found that running the ES membrane probe with specific Electrolytes in the second solution of the ES membrane probe have been found to enhance ESMS signal compared to using the same electrolytes directly in the sample solution being Electrosprayed. The new electrolytes can be added to a reagent ion source configured in a combination Atmospheric pressure ion source to improve ionization efficiency.

摘要翻译： 与质谱仪接口的电喷雾离子源已成为分析应用中广泛使用的工具。 在电喷雾（ES）电离中发生的过程通常包括加入或除去诸如H +或其它阳离子的带电物质以实现样品物质的离子化。 电喷雾包括在液相和气相中发生的电离过程，并且在两相中，电离过程需要这种带电物质的源或汇。 有助于在电喷雾电离中发生的氧化或还原反应的电解质物质被添加到许多分析应用中的样品溶液中，以增加在电喷雾中产生的离子信号幅度，并通过质谱仪（MS）检测可能需要增强的电解质物质 上游样品制备或分离过程可能与下游ES过程较不相容，并导致MS信号的降低。 已经发现新的电解质在ESMS分析中测量的正极和负极性分析物离子信号与使用更常规电解质获得的分析物ESMS信号相比较。 新的电解质物质直接添加到样品溶液中或当添加到电喷雾膜探针中的第二溶液流中时，增加ES MS信号。 已经发现，与在电喷雾的样品溶液中直接使用相同电解质相比，已经发现在ES膜探针的第二溶液中使用特定电解质的ES膜探针增强ESMS信号。 可以将新的电解质添加到以大气压离子源组合的试剂离子源中，以提高电离效率。

公开(公告)号：US20090095899A1

公开(公告)日：2009-04-16

申请号：US12251023

申请日：2008-10-14

申请人： Craig M. Whitehouse ,  Thomas White ,  Shida Shen

发明人： Craig M. Whitehouse ,  Thomas White ,  Shida Shen

IPC分类号： B01D59/44

CPC分类号： H01J49/165 ,  Y10T436/24

摘要： Electrospray ionization sources interfaced to mass spectrometers have become widely used tools in analytical applications. Processes occurring in Electrospray (ES) ionization generally include the addition or removal of a charged species such as H+ or other cation to effect ionization of a sample species. Electrospray includes ionization processes that occur in the liquid and gas phase and in both phases ionization processes require a source or sink for such charged species. Electrolyte species, that aid in oxidation or reduction reactions occurring in Electrospray ionization, are added to sample solutions in many analytical applications to increase the ion signal amplitude generated in Electrospray and detected by a mass spectrometer (MS) Electrolyte species that may be required to enhance an upstream sample preparation or separation process may be less compatible with the downstream ES processes and cause reduction in MS signal New Electrolytes have been found that increase positive and negative polarity analyte ion signal measured in ESMS analysis when compared with analyte ESMS signal achieved using more conventional electrolytes The new electrolyte species increase ES MS signal when added directly to a sample solution or when added to a second solution flow in an Electrospray membrane probe. It has also been found that running the ES membrane probe with specific Electrolytes in the second solution of the ES membrane probe have been found to enhance ESMS signal compared to using the same electrolytes directly in the sample solution being Electrosprayed The new electrolytes can be added to a reagent ion source configured in a combination Atmospheric pressure ion source to improve ionization efficiency.

摘要翻译： 与质谱仪接口的电喷雾离子源已成为分析应用中广泛使用的工具。 在电喷雾（ES）电离中发生的过程通常包括加入或除去诸如H +或其它阳离子的带电物质以实现样品物质的离子化。 电喷雾包括在液相和气相中发生的电离过程，并且在两相中，电离过程需要这种带电物质的源或汇。 有助于在电喷雾电离中发生的氧化或还原反应的电解质物质被添加到许多分析应用中的样品溶液中，以增加在电喷雾中产生的离子信号幅度，并通过质谱仪（MS）检测可能需要增强的电解质物质 上游样品制备或分离过程可能与下游ES过程不太相容并导致MS信号的降低新电解质已经发现，当与使用更常规的分析物达到的分析物ESMS信号相比时，ESMS分析中测量的正极和负极性分析物离子信号增加 电解质新的电解质物质直接添加到样品溶液中或当添加到电喷雾膜探针中的第二溶液流时，增加ES MS信号。 已经发现，在ES膜探针的第二溶液中使用特定电解质的ES膜探针已经被发现增强ESMS信号，与在电喷雾的样品溶液中直接使用相同的电解质相比可以将新的电解质添加到 组合大气压离子源的试剂离子源，提高电离效率。

公开(公告)号：US20080047330A1

公开(公告)日：2008-02-28

申请号：US11895494

申请日：2007-08-24

申请人： Craig M. Whitehouse ,  Thomas White

发明人： Craig M. Whitehouse ,  Thomas White

IPC分类号： G01N30/02 ,  G01N21/01 ,  G01N27/30

CPC分类号： B01D59/44 ,  G01N1/4005 ,  G01N30/00 ,  G01N30/7266 ,  H01J49/165 ,  Y10T436/212 ,  Y10T436/24

摘要： The invention provides a method and apparatus for trapping, releasing and/or separating sample components in solution passing through a channel with or without packing material present by passing ion current through the channel driven by an electric field. A portion of the ion current comprises cation and/or anion species generated from second solution flows separated from the sample solution flow path by semipermeable membranes. Cation and/or Anion ion species generated in the second solution flow regions are transferred into the sample solution flow path through ion selective semipermeable membranes. Ion current moving along the sample solution flow path is controlled by varying the composition of the second solutions and/or changing the voltage between membrane sections for a given sample solution composition. The sample composition may also be varied separately or in parallel to enhance trapping, release and/or separation efficiency and range. The invention when interfaced to an Atmospheric Pressure Ion Source, that may include Electrospray Ionization, with mass spectrometric analysis enables independent control of the on-line sample separation process and the Atmospheric Pressure Ion Source or Electrospray ionization processes.

摘要翻译： 本发明提供了一种用于通过使通过离子电流通过由电场驱动的通道而使存在的填充材料通过通道的溶液中的样品组分的捕获，释放和/或分离的方法和装置。 离子电流的一部分包括由通过半透膜从样品溶液流动路径分离的第二溶液流产生的阳离子和/或阴离子物质。 在第二溶液流动区域中产生的阳离子和/或阴离子物质通过离子选择性半透膜转移到样品溶液流动路径中。 沿着样品溶液流动路径移动的离子电流通过改变第二溶液的组成和/或改变给定样品溶液组合物的膜部分之间的电压来控制。 样品组合物也可以单独地或并行地改变以提高捕获，释放和/或分离效率和范围。 当与质谱分析相结合的可能包括电喷雾离子化的大气压力离子源的本发明可以独立控制在线样品分离过程和大气压力离子源或电喷雾离子化过程。

公开(公告)号：US07919746B2

公开(公告)日：2011-04-05

申请号：US12251058

申请日：2008-10-14

申请人： Craig M. Whitehouse ,  Thomas White ,  Shida Shen

发明人： Craig M. Whitehouse ,  Thomas White ,  Shida Shen

IPC分类号： H01J49/04 ,  G01N30/72

CPC分类号： H01J49/165 ,  Y10T436/24

摘要： The instant invention deals with species that may be required to enhance an upstream sample preparation or separation process may be less compatible with the downstream ES processes and cause reduction in MS signal. New electrolytes have been found that increase positive and negative polarity analyte ion signal measured in ESMS analysis when compared with analyte ESMS signal achieved using more conventional electrolytes. The new electrolyte species increase ES MS signal when added directly to a sample solution or when added to a second solution flow in an electrospray membrane probe, it has also been found that running the ES membrane probe with specific electrolytes in the second solution of the ES membrane probe have been found to enhance ESMS signal compared to using the same electrolytes directly in the sample solution being electrosprayed. The new electrolytes can be added to a reagent ion source configured in a combination atmospheric pressure ion source to improve ionization efficiency.

摘要翻译： 本发明涉及增强上游样品制备或分离过程可能需要的物种可能与下游ES过程较不相容并导致MS信号的降低。 已经发现，与使用更常规电解质实现的分析物ESMS信号相比，在ESMS分析中测量的新的电解质增加了正极和负极性分析物离子信号。 当新的电解质物质直接添加到样品溶液中时，或者当添加到电喷雾膜探针中的第二溶液流中时，新的电解质物质增加ES MS信号。 已经发现，与在电喷雾的样品溶液中直接使用相同的电解质相比，已经发现在ES膜探针的第二溶液中使用特定电解质的ES膜探针增强ESMS信号。 可以将新的电解质添加到组合大气压离子源中的试剂离子源，以提高电离效率。

公开(公告)号：US20110220789A1

公开(公告)日：2011-09-15

申请号：US13006934

申请日：2011-01-14

申请人： Craig M. Whitehouse ,  Thomas White

发明人： Craig M. Whitehouse ,  Thomas White

IPC分类号： H01J49/26

CPC分类号： B01D59/44 ,  G01N1/4005 ,  G01N30/00 ,  G01N30/7266 ,  H01J49/165 ,  Y10T436/212 ,  Y10T436/24

摘要： The invention provides a method and apparatus for trapping, releasing and/or separating sample components in solution passing through a channel with or without packing material present by passing ion current through the channel driven by an electric field. A portion of the ion current comprises cation and/or anion species generated from second solution flows separated from the sample solution flow path by semipermeable membranes. Cation and/or Anion ion species generated in the second solution flow regions are transferred into the sample solution flow path through ion selective semipermeable membranes. Ion current moving along the sample solution flow path is controlled by varying the composition of the second solutions and/or changing the voltage between membrane sections for a given sample solution composition. The sample composition may also be varied separately or in parallel to enhance trapping, release and/or separation efficiency and range. The invention when interfaced to an Atmospheric Pressure Ion Source, that may include Electrospray Ionization, with mass spectrometric analysis enables independent control of the on-line sample separation process and the Atmospheric Pressure Ion Source or Electrospray ionization processes.

摘要翻译： 本发明提供了一种用于通过使通过离子电流通过由电场驱动的通道而使存在的填充材料通过通道的溶液中的样品组分的捕获，释放和/或分离的方法和装置。 离子电流的一部分包括由通过半透膜从样品溶液流动路径分离的第二溶液流产生的阳离子和/或阴离子物质。 在第二溶液流动区域中产生的阳离子和/或阴离子物质通过离子选择性半透膜转移到样品溶液流动路径中。 沿着样品溶液流动路径移动的离子电流通过改变第二溶液的组成和/或改变给定样品溶液组合物的膜部分之间的电压来控制。 样品组合物也可以单独地或并行地改变以提高捕获，释放和/或分离效率和范围。 当与质谱分析相结合的可能包括电喷雾离子化的大气压力离子源的本发明可以独立控制在线样品分离过程和大气压力离子源或电喷雾离子化过程。

公开(公告)号：US08378295B2

公开(公告)日：2013-02-19

申请号：US13078578

申请日：2011-04-01

申请人： Craig M. Whitehouse ,  Thomas White ,  Shida Shen

发明人： Craig M. Whitehouse ,  Thomas White ,  Shida Shen

IPC分类号： B01D59/44

CPC分类号： H01J49/165 ,  Y10T436/24

摘要： Species that may be required to enhance an upstream sample preparation or separation process may be less compatible with the downstream electrospray (ES) processes and cause reduction in mass spectroscopy (MS) signal. New electrolytes have been found that increase positive and negative polarity analyte ion signal measured in ESMS analysis when compared with analyte ESMS signal achieved using more conventional electrolytes. The new electrolyte species increase ES MS signal when added directly to a sample solution or when added to a second solution flow in an electrospray membrane probe, it has also been found that running the ES membrane probe with specific electrolytes in the second solution of the ES membrane probe have been found to enhance ESMS signal compared to using the same electrolytes directly in the sample solution being electrosprayed. The new electrolytes can be added to a reagent ion source configured in a combination atmospheric pressure ion source to improve ionization efficiency.

摘要翻译： 增强上游样品制备或分离过程可能需要的物质可能与下游电喷雾（ES）过程较不相容，并导致质谱（MS）信号的降低。 已经发现，与使用更常规电解质实现的分析物ESMS信号相比，在ESMS分析中测量的新的电解质增加了正极和负极性分析物离子信号。 当直接添加到样品溶液中时，或当添加到电喷雾膜探针中的第二溶液流中时，新的电解质物质增加ESMS信号，还已经发现在ES膜的第二溶液中运行具有特定电解质的ES膜探针 已经发现与在电喷雾的样品溶液中直接使用相同的电解质相比，探针增强了ESMS信号。 可以将新的电解质添加到组合大气压离子源中的试剂离子源，以提高电离效率。